Carbonate precursors for lithium nickel manganese cobalt oxide cathode material and the method of making same

Patent metadata

Field	Value
Publication number	US-11380882-B2
Application number	US-201515517276-A
Country	US
Kind code	B2
Filing date	Sep 30, 2015
Priority date	Oct 8, 2014
Publication date	Jul 5, 2022
Grant date	Jul 5, 2022

Abstract

A method for producing a M-carbonate precursor of a Li-M oxide cathode material in a continuous reactor, wherein M=NixMnyCozAn, A being a dopant, with x>0, y>0, 0≤z≤0.35, 0≤n≤0.02 and x+y+z+n=1, the method comprising the steps of: —providing a feed solution comprising Ni-, Mn-, Co- and A-ions, and having a molar metal content M″ feed, —providing an ionic solution comprising either one or both of a carbonate and a bicarbonate solution, the ionic solution further comprising either one or both of Na- and K-ions, —providing a slurry comprising seeds comprising M′-ions and having a molar metal content M′ seeds, wherein M′=Nix′Mny′Coz′A′n′, A′ being a dopant, with 0≤x′≤1, 0≤y′≤1, 0≤z′≤1, 0≤n′≤1 and x′+y′+z′+n′=1, and wherein the molar ratio M′ seeds/M″ feed is between 0.001 and 0.1, —mixing the feed solution, the ionic solution and the slurry in the reactor, thereby obtaining a reactive liquid mixture, —precipitating a carbonate onto the seeds in the reactive liquid mixture, thereby obtaining a reacted liquid mixture and the M-carbonate precursor, and —separating the M-carbonate precursor from the reacted liquid mixture.

First claim

The invention claimed is:

1. A method for producing a M-carbonate precursor of a Li-M oxide cathode material in a continuous process in a reactor, wherein M=Ni x Mn y Co z A n , A being a dopant, with x>0, y>0, 0≤z≤0.35, 0≤n≤0.02 and x+y+z+n=1, the method comprising:
introducing to the reactor a feed solution comprising Ni-, Mn-, Co- and A-ions, wherein the feed solution contains a total amount of Ni-, Mn-, Co- and A-ions £M″ feed ),
introducing to the reactor an ionic solution comprising either one or both of a carbonate and a bicarbonate solution, the ionic solution further comprising either one or both of Na- and K-ions,
pumping a slurry comprising seeds into the reactor, the seeds comprising M′-ions, wherein the slurry contains a total amount of M′ ions (M′ seeds ), wherein M′=Ni x′ Mn y′ Co z′ A′ n′ , A′ being a dopant, with 0≤x′≤1, 0≤y′≤1, 0≤z′≤1, 0≤n′≤1 and x′+y′+z′+n′=1, and wherein the molar ratio M′ seeds /M″ feed is between 0.001 and 0.04,
mixing the feed solution, the ionic solution and the slurry in the reactor, thereby obtaining a reactive liquid mixture,
precipitating a carbonate onto the seeds in the reactive liquid mixture, thereby obtaining a reacted liquid mixture and the M-carbonate precursor, and
separating the M-carbonate precursor from the reacted liquid mixture.

2. The method according to claim 1 , wherein the seeds have a median particle size D50 between 0.1 and 3 μm.

3. The method according to claim 1 , wherein the M′-ions are present in a water insoluble compound that is selected from the group consisting of M′CO 3 , M′(OH) 2 , M′-oxide and MOOH.

4. The method according to claim 3 , wherein the water insoluble compound is either MnCO 3 or TiO 2 .

5. The method according to claim 1 , wherein the Ni-, Mn-, Co- and A-ions are present in a water soluble sulfate compound.

6. The method according to claim 1 , wherein a concentration of NH 3 in the reactor is less than 5.0 g/L.

7. The method according to claim 1 , wherein M=M′.

8. The method according to claim 1 , wherein the solid content in the slurry flow is between 30 and 300 g/L.

9. The method according to claim 1 , wherein the reactor is a continuous stirred tank reactor (CSTR).

10. The method according to claim 1 , further comprising the step of drying the separated M-carbonate precursor, wherein the dried M-carbonate precursor has a span defined as the value of (D90−D10)/D50 of its volumetric particle size distribution, and wherein the ratio M′ seeds /M″ feed is ≤0.01, such that a span<2 of the dried M-carbonate precursor is obtained.

11. A method for producing a lithium M-oxide cathode material for a rechargeable battery, comprising:
providing a M-carbonate precursor by the method according to claim 1 ,
providing a Li precursor compound,
mixing the M-carbonate and the Li precursor, and
firing the mixture at a temperature between 600 and 1100° C. for at least 1 hr.

12. A method for producing a lithium M-oxide cathode material for a rechargeable battery, comprising:
providing a M-carbonate precursor by the method according to claim 5 ,
providing a Li precursor compound,
mixing the M-carbonate and the Li precursor, and
firing the mixture at a temperature between 600 and 1100° C. for at least 1 hr.

13. A method for producing a lithium M-oxide cathode material for a rechargeable battery, comprising:
providing a M-carbonate precursor by the method according to claim 3 ,
providing a Li precursor compound,
mixing the M-carbonate and the Li precursor, and
firing the mixture at a temperature between 600 and 1100° C. for at least 1 hr.

14. A method for producing a lithium M-oxide cathode material for a rechargeable battery, comprising:
providing a M-carbonate precursor by the method according to claim 7 ,
providing a Li precursor compound,
mixing the M-carbonate and the Li precursor, and
firing the mixture at a temperature between 600 and 1100° C. for at least 1 hr.

15. A method for producing a lithium M-oxide cathode material for a rechargeable battery, comprising:
providing a M-carbonate precursor by the method according to claim 10 ,
providing a Li precursor compound,
mixing the M-carbonate and the Li precursor, and
firing the mixture at a temperature between 600 and 1100° C. for at least 1 hr.

Assignees

• Umicore Nv
• Umicore Korea Ltd

Inventors

• Hu Jin
• Hong Heonpyo
• Paulsen Jens
• Oh Jindoo
• Nelis Daniël
• Robert Eric

Classifications

• C01G53/82 Primary

  Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• C01P2006/11

  Powder tap density · CPC title

• H01M4/485

  of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) · CPC title

• C01P2006/40

  Electric properties · CPC title